CN109678681A - 一种制备卤代联苯的方法 - Google Patents

一种制备卤代联苯的方法 Download PDF

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CN109678681A
CN109678681A CN201910036180.1A CN201910036180A CN109678681A CN 109678681 A CN109678681 A CN 109678681A CN 201910036180 A CN201910036180 A CN 201910036180A CN 109678681 A CN109678681 A CN 109678681A
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谢劲
朱成建
刘凯
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Abstract

一种制备卤代联苯类化合物的方法，它是以芳基硼酸酯和芳基硅烷试剂为原料，1,1,2‑三氯乙烷作为溶剂，醋酸碘苯作为氧化剂，对甲苯磺酸银作为银盐。在110℃下，N‑(二苯基磷烷基)‑N‑异丙基‑1,1‑二苯基膦胺双核金1a催化交叉偶联，高效合成卤代联芳基类化合物的方法。

Description

一种制备卤代联苯的方法
技术领域
本发明涉及一种制备卤代联苯类化合物的方法。
背景技术
联苯结构单元普遍存在于许多科学领域分子中(如农用化学品，药品和先进的有机材料)[参见：(a)Angew.Chem.Int.Ed.2012，51,5062.(b)Nat.Rev.Chem.2017，1,0025.]。尽管制备这类化合物有许多合成策略[参见：(a)Science 2006，313,662-664.(b)Nature2018，563,100-104.(c)Nature 2015，519,334-338.],但是钯和镍催化的亲电子试剂(芳基卤化物，Ar1-X，X＝Cl，Br，I，OTf等)和亲核试剂(芳基有机金属，Ar2-M)之间的交叉偶联一直是该领域研究的焦点。然而，钯和镍催化剂的高催化活性也导致对一些官能团的容性存在固有的限制。近年来，均相金催化[参见：A.Hashmi,S.K.Toste,D.F.Eds,Modern GoldCatalyzed Synthesis(Wiley-VCH,2012)]表现出优异的官能团和生物分子相容性以及环境友好特征而受到广泛关注[参见：Malta G.et al.Science 355,1399–1403(2017)]。最近报道的金催化的合成策略主要涉及富电子芳烃的C-H芳基化[参见：(a)Science 2012,337,1644-1648.(b)J.Am.Chem.Soc.2015,137,15636-15639.(c)Angew.Chem.Int.Ed.2017,56,1021-1025.]，而这种选择性严重依赖于底物的电子性质(给电子基团的邻位和对位)。因此，金催化定点交叉偶联合成联芳基类化合物仍然是一个重大的挑战。采用芳基硼酸酯和芳基硅烷试剂作为偶联剂，具有广泛的应用性，商业可用性，空气下稳定性和无毒性等特点。在无外加碱的条件下，金催化这两种偶联剂可以定点高效交叉偶联反应，同时也加速了联芳基类药物的合成。
发明内容
本发明要解决的技术问题是提供一种制备卤代联苯类化合物的方法以及其应用。
本发明的合成路线如下：
一种卤代联苯类化合物的制备方法，它是以FG2和X取代的芳基硼酸酯(2)及FG1和X取代的芳基硅烷试剂(1)为原料，以1,1,2-三氯乙烷作为溶剂，醋酸碘苯((Diacetoxyiodo)benzene)作为氧化剂，对甲苯磺酸银(Silver p-toluenesulfonate)作为银盐，在110℃下，以N-(二苯基磷烷基)-N-异丙基-1,1-二苯基膦胺双核金(Dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine)digold(I))1a作为金催化剂，高效合成保有卤代、FG1基和FG1基的联芳基类化合物。
上述的制备方法，所述的FG1基团可以是氢、烷基、磺酸酯基、炔基、硅醚、醇羟基或甲酸酯基等；FG2基团可以氢、卤素、醛基、羧酸、酰胺或缩醛等；X基团可以是各种取代的卤素和类卤素(I、Br、Cl、CN、OTf或OMs etc)。
上述的制备方法，所述的N-(二苯基磷烷基)-N-异丙基-1,1-二苯基膦胺双核金(1a)有如下结构：
上述的制备方法，所述的溶剂1,1,2-三氯乙烷是分子筛预处理过的。
上述的制备方法，所述的芳基硅烷试剂和芳基硼酸酯的摩尔比是1:1-1:2，最佳为1:1.3。
上述的制备方法，所述的金催化剂1a的用量是芳基硅烷试剂1摩尔数的5％-10％；银盐催化剂的用量是芳基硅烷试剂1摩尔数的20％-40％。
上述的制备方法，所述的醋酸碘苯是芳基硅烷试剂1摩尔数的1-2倍，1.3倍最佳。
典型反应如下：
本发明的方法只需一个偶联底物稍微过量即可突破富电子芳烃的邻对位取向规则，并具有优异的官能团兼容性和灵活的合成能力。同时这种策略加速了有机金属试剂交叉偶联，避免了在药物制备过程中钯和镍金属残留。
具体实施方式
金催化剂1a是按照文献(Angew.Chem.Int.Ed.2014，53,6211-6215.)进行合成的。
原料的合成：
原料芳基硼酸酯和芳基硅烷试剂是根据文献制备的
的制备[参见：J.Am.Chem.Soc.2007,129,15919.]：
称取(0.83g,5mmol)溶于20ml二氯甲烷溶液中，冷却到0℃，滴加入Et3N(1.4mL,10mmol)，接着向反应液中再滴入甲磺酰氯(0.78mL,10mmol)。然后，反应混合溶液在室温下搅拌过夜。后处理过程中，向反应溶液中加入饱和NaHCO3(15mL)，二氯甲烷(3×20mL)萃取，有机相用无水硫酸钠干燥，过滤旋干。通过柱层析(300-400目层析硅胶，下同)分离(石油醚-乙酸乙酯＝7:1)得到产物0.93g，产率76％。1H NMR(500MHz,CDCl3)δ7.48–7.45(m,1H),7.40(t,J＝10.0Hz,1H),7.38-7.36(m,1H),7.28-7.25(m,1H),3.14(s,3H),0.28(s,9H).13C NMR(125MHz,CDCl3)δ149.1,143.9,132.2,129.5,126.3,122.2,37.4,-1.3.
称取(1.50g,10.0mmol)(萨恩化学技术(上海)有限公司提供，下同)和(2.29g,22.0mmol)(萨恩化学技术(上海)有限公司提供，下同)，并加入装有50ml的甲苯溶液的反应瓶中，利用分水器进行回流过夜。反应液被浓缩，利用柱层析方法进行分离(流动相石油醚：乙酸乙酯＝20:1)得到目标产物2.07g,产率68％。1H NMR(400MHz,CDCl3)δ7.96-7.88(m,1H),7.78(d,J＝8.0Hz,1H),7.59(d,J＝8.0Hz,1H),7.37(t,J＝8.0Hz,1H),5.40(s,1H),3.79-3.74(m,6H),3.64(d,J＝12.0Hz,2H),1.30(s,3H),1.01(s,6H),0.79(s,3H).13CNMR(125MHz,CDCl3)δ137.6,134.4,131.6,128.4,127.6,102.1,77.7,72.3,31.9,30.3,23.2,22.0,21.9.
先称取(2.06g,10mmol)[参见：PCT Int.Appl.(2007),WO2007102126 A2 20070913]，加入装有30ml四氢呋喃溶液的反应瓶中，冷却到0℃，分批加入氢化钠(60％w/t在煤油中,0.60g,15mmol)(萨恩化学技术(上海)有限公司提供)。在0℃下搅拌30分钟，接着将(1.57g,15mmol)(萨恩化学技术(上海)有限公司提供)缓慢滴入到反应液中。反应液转到室温下搅拌4h,加入冰水猝灭反应。然后，利用乙酸乙酯(3×20mL)萃取，无水硫酸钠干燥，浓缩，利用柱层析分离(流动相石油醚：乙酸乙酯)目标产物2.25g,产率82％。1H NMR(400MHz,CDCl3)δ7.72-7.62(m,1H),7.60-7.47(m,1H),7.37(t,J＝8.0Hz,1H),7.25-7.07(m,2H),6.11-5.98(m,1H),3.75(s,4H),1.96(dd,J＝8.0,4.0Hz,3H),1.01(s,6H).13C NMR(100MHz,CDCl3)δ165.0,150.4,146.6,131.1,128.7,126.7,123.9,122.2,72.3,31.9,21.9,18.2.
利用下述实施例将有助于理解本发明，但并不限制本发明的内容。
实施例1
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(上海凌峰化学试剂有限公司提供，下同。)(1ml),并在室温条件下剧烈搅拌30min。随后(55.2mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物44.3mg(石油醚)，产率70％。1H NMR(500MHz,CDCl3)δ7.77-7.74(m,2H),7.35(t,J＝10.0Hz,1H),7.33-7.31(m,2H),7.15-7.11(m,1H),7.07(t,J＝5.0Hz,1H),6.93-6.89(m,1H),3.86(s,3H).13C NMR(125MHz,CDCl3)δ160.0,141.6,140.6,137.8,129.9,129.0,119.4,113.0,112.7,100.0,93.2,55.4.IR(ATR):ν＝2955,2919,2850,1474,1429,1293,1248,1049,1024,1002,818,774,692cm- 1.HRMS(EI)calcd for C13H11IO(M+):309.9855,found 309.9856
实施例2
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(45.8mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物38.4mg(石油醚：乙酸乙酯＝100:1)，产率73％。1H NMR(500MHz,CDCl3)δ7.56(d,J＝10.0Hz,2H),7.45(d,J＝10.0Hz,2H),7.36(t,J＝10.0Hz,1H),7.17-7.12(m,1H),7.08(t,J＝5.0Hz,1H),6.96-6.90(m,1H),3.87(s,3H).13C NMR(125MHz,CDCl3)δ160.0,141.5,140.0,131.9,129.9,128.8,121.7,119.5,113.0,112.8,55.4.
实施例3
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物40.5mg(石油醚：乙酸乙酯＝100:1)，产率61％。1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,1H),7.27(d,J＝8.0Hz,2H),7.09-7.45(m,1H),7.01(t,J＝4.0,1H),6.90-6.83(m,1H),3.80(s,3H).19F NMR(376MHz,CDCl3)δ-72.78.13C NMR(101MHz,CDCl3)δ160.1,149.0,141.6,140.8,130.0,128.9,121.6,120.6,119.7,113.3,113.1,55.4.HRMS(EI)calcd for C14H11F3O4S(M+):332.0330,found332.0324.
实施例4
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(35.7mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物24.2mg(石油醚：乙酸乙酯＝100:1)，产率57％。1H NMR(500MHz,CDCl3)δ7.51(d,J＝10.0Hz,2H),7.34(t,J＝10.0Hz,1H),7.27(d,J＝10.0Hz,2H),7.19-7.15(m,1H),7.12(t,J＝5.0Hz,1H),6.88(dd,J＝10.0,5.0Hz,1H),3.86(s,3H),2.70(q,J＝10.0Hz,2H),1.28(t,J＝10.0Hz,3H).13C NMR(125MHz,CDCl3)δ159.9,143.6,142.7,138.5,129.7,128.3,127.1,119.6,112.7,112.4,55.3,28.5,15.6.IR(ATR):ν＝2958,2923,2852,1620,1601,1573,1564,856,831,768,750,695cm-1.HRMS(EI)calcd for C15H16O(M+):212.1201,found 212.1196.
实施例5
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(35.1mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物21.8mg(石油醚：乙酸乙酯＝40:1-30:1)，产率52％。1H NMR(500MHz,CDCl3)δ7.74-7.70(m,2H),7.69-7.66(m,2H),7.40(t,J＝10.0Hz,1H),7.19-7.15(m,1H),7.11(t,5.0Hz,1H),6.99-6.94(m,1H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ160.1,145.6,140.7,132.6,130.2,127.8,119.7,118.9,113.9,113.1,111.0,55.4.
实施例6
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(41.7mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物33.9mg(石油醚：乙酸乙酯＝30:1)，产率70％。1H NMR(500MHz,CDCl3)δ8.10(d,J＝5.0Hz,2H),7.65(d,J＝5.0Hz,2H),7.41-7.35(m,1H),7.23-7.19(m,1H),7.15(t,J＝2.2Hz,1H),6.94(dd,J＝8.2,2.4Hz,1H),3.94(d,J＝0.9Hz,3H),3.88(d,J＝0.9Hz,3H).13C NMR(125MHz,CDCl3)δ167.0,160.0,145.5,141.5,130.1,130.0,129.0,127.1,119.8,113.5,113.0,55.4,52.2.
实施例7
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(41.7mg,0.2mmol)和(TIPS是i-Pr3Si基团)(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物44.2mg(石油醚：乙酸乙酯＝100:1)，产率62％。1H NMR(500MHz,CDCl3)δ7.45(d,J＝10.0Hz,2H),7.32(t,J＝10.0Hz,1H),7.16-7.12(m,1H),7.09(t,J＝5.0Hz,1H),6.93(d,J＝10.0Hz,2H),6.86-6.82(m,1H),3.86(s,3H),1.30-1.25(m,3H),1.13(s,9H),1.10(s,9H).13C NMR(125MHz,CDCl3)δ159.9,155.8,142.4,133.8,129.7,128.1,120.1,119.3,112.4,112.0,55.3,18.0,12.7.IR(ATR):ν＝2945,2927,2867,1606,1516,1480,1270,1220,1212,914,883,834,689cm-1.HRMS(EI)calcd for C22H32O2Si(M+):356.2172,found 356.2170.
实施例8
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(48.9mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物35.6mg(石油醚：乙酸乙酯＝7:1)，产率64％。1H NMR(500MHz,CDCl3)δ7.57-7.53(m,1H),7.50-7.46(m,2H),7.37(t,J＝10.0Hz,1H),7.29-7.26(m,1H),7.18-7.13(m,1H),7.10(t,J＝5.0,1H),6.95-6.91(m,1H),3.87(s,3H),3.17(s,3H).13C NMR(125MHz,CDCl3)δ160.1,149.6,143.4,141.0,130.3,130.0,126.2,120.8,119.7,113.4,113.0,55.4,37.5.IR(ATR):ν＝2921,2851,1601,1573,1364,1330,1218,1177,1140,968,870,837,779cm-1.HRMS(EI)calcd for C14H14O4S(M+):278.0613,found278.0621.
实施例9
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(38.9mg,0.2mmol)和(57.2mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物22.8mg(石油醚：乙酸乙酯＝5:1)，产率50％。1H NMR(500MHz,CDCl3)δ7.36-7.30(m,3H),7.29-7.26(m,1H),7.25-7.22(m,1H),6.92-6.87(m,2H),6.86(t,J＝5.0Hz,1H),3.83(s,3H),3.72-3.66(m,2H),2.89(t,J＝5.0Hz,2H),1.27(t,J＝5.0Hz,1H).13C NMR(125MHz,CDCl3)δ159.3,143.0,142.4,135.6,130.2,129.8,129.2,127.6,126.4,121.7,114.9,112.5,63.4,55.3,36.3.
实施例10
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(129mg,0.4mmol)和DCM(1ml),并在室温条件下剧烈搅拌30min。随后(50.1mg,0.2mmol)和(57.2mg,0.26mmol)的DCM(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物26.7mg(石油醚：乙酸乙酯＝100:1)，产率47％。1H NMR(500MHz,CDCl3)δ7.63-7.60(m,1H),7.59(d,J＝5.0Hz,3H),7.57-7.54(m,2H),7.39-7.34(m,4H),7.22-7.18(m,1H),7.14(t,J＝5.0Hz,1H),6.92(dd,J＝10.0,5.0Hz,1H),3.88(s,3H).13CNMR(125MHz,CDCl3)δ160.0,141.9,140.8,132.0,131.6,129.9,128.4,128.3,127.1,123.3,122.3,119.5,113.0,112.7,90.1,89.3,55.4.
实施例11
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(82.15mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物71.9mg(石油醚：乙酸乙酯＝100:1)，产率84％。
1H NMR(400MHz,CDCl3)δ7.79(d,J＝8.0Hz,2H),7.60(d,J＝8.0Hz,2H),7.34(d,J＝8.0Hz,2H),7.29(d,J＝8.0Hz,2H).19F NMR(471MHz,)δ-72.75.13C NMR(100MHz,CDCl3)δ149.1,140.6,138.8,138.1,129.0,128.7,123.6,121.9,120.4,117.2,114.0,94.1.IR(ATR):ν＝1475,1417,1385,1201,1133,1058,1019,884,809,603,573,519,491cm-1.HRMS(EI)calcd for C13H8F3IO3S(M+):427.9191,found 427.9183.
实施例12
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(70.0mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物59.5mg(石油醚：乙酸乙酯＝100:1)，产率78％。
1H NMR(500MHz,CDCl3)δ7.60(t,J＝10.0Hz,4H),7.42(d,J＝10.0Hz,2H),7.35(d,J＝10.0Hz,2H).19F NMR(471MHz,CDCl3)δ-72.75.13C NMR(125MHz,CDCl3)δ149.11,140.49,138.19,132.15,128.77,128.74,122.58,122.50,121.84,120.03,117.48,114.93.
实施例13
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(67.1.0mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物54.8mg(石油醚：乙酸乙酯＝100:1)，产率74％。1H NMR(500MHz,CDCl3)δ7.73(d,J＝10.0Hz,2H),7.69-7.64(m,4H),7.39(d,J＝10.0Hz,2H).19FNMR(471MHz,CDCl3)δ-62.56,-72.74.13C NMR(125MHz,CDCl3)δ149.5,142.8,140.2,131.3,130.6,130.3,130.1,129.8,129.1,127.6,126.0,126.0,126.0,125.9,122.6,122.0,120.0,117.5,114.9.
实施例14
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(129mg,0.4mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(56.7mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过柱层析分离得到产物52.8mg(石油醚：乙酸乙酯＝40:1)，产率80％。
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.08(t,J＝5.0Hz,1H),7.93-7.89(m,1H),7.85-7.81(m,1H),7.69(d,J＝10.0Hz,2H),7.65(t,J＝10.0Hz,1H),7.39(d,J＝10.0Hz,2H).19F NMR(471MHz,CDCl3)δ-72.74.13C NMR(125MHz,CDCl3)δ192.0,149.4,140.3,140.2,137.1,133.0,129.8,129.6,129.0,128.0,122.6,122.0,120.0,117.5,114.9.IR(ATR):ν＝1698,1420,1204,1133,1015,879,843,604cm-1.HRMS(EI)calcd for C14H9F3O4S(M+):330.0174,found 330.0168.
实施例15
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(55.9mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物39.3mg(石油醚：乙酸乙酯＝50:1-40:1)，产率60％。1H NMR(400MHz,CDCl3)δ7.84(t,J＝5.0Hz,1H),7.79(dt,J＝10.0,5.0Hz,1H),7.69(dt,J＝10.0,5.0Hz,1H),7.64(d,J＝10.0Hz,2H),7.59(t,J＝10.0Hz,1H),7.40(d,J＝10.0Hz,2H).19F NMR(376MHz,CDCl3)δ-72.72.13C NMR(100MHz,CDCl3)δ149.6,140.6,139.3,131.5,130.7,129.9,129.0,123.5,122.1,120.4,118.5,117.2,114.1,113.3.IR(ATR):ν＝2955,2918,2850,1462,1206,1135,1015,840,778,749,723,604,527cm-1.HRMS(EI)calcd forC14H8F6NO3S(M+):327.0177,found 327.0174.
实施例16
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(78.3mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应10h。反应液浓缩，干法上样，柱层析得到产物33.9mg(石油醚：乙酸乙酯＝5:1-4:1)，产率41％。1H NMR(500MHz,CDCl3)δ7.96(t,J＝5.0Hz,1H),7.72(dt,J＝10.0,5.0Hz,1H),7.67(d,J＝10.0Hz,3H),7.51(t,J＝10.0Hz,1H),7.36(d,J＝10.0Hz,2H),6.13(d,J＝10.0Hz,1H),4.50-4.37(m,1H),2.16-2.08(m,2H),1.78-1.65(m,4H),1.55-1.48(m,2H).19F NMR(471MHz,CDCl3)δ-72.74.13C NMR(125MHz,CDCl3)δ166.8,149.2,140.8,139.8,135.8,129.9,129.2,129.0,126.1,126.1,122.6,121.8,120.0,117.5,114.9,51.9,33.3,23.9.IR(ATR):ν＝3272,2956,2923,2868,1629,1509,1418,1250,1206,1136,896,841,809,702,664,639,521cm-1.HRMSm/z(ESI)calcd for C19H19F3NO4S(M+H)+414.0981,found:414.0979.
实施例17
干燥的封管中加入金催化剂1a(17.8mg,0.02mmol)，AgOTs(22.3mg,0.08mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(71.3mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物51.8mg(石油醚：乙酸乙酯＝40:1-30:1)，产率67％。1HNMR(400MHz,CDCl3)δ7.62(d,J＝8.0Hz,2H),7.46(t,J＝8.0Hz,1H),7.44-7.39(m,1H),7.33(d,J＝8.0Hz,2H),7.31(t,J＝4.0Hz,1H),7.27-7.17(m,1H),7.17-7.11(m,1H),6.15-6.00(m,1H),1.98(dd,J＝8.0,4.0Hz,3H).19F NMR(376MHz,CDCl3)δ-72.78.13C NMR(125MHz,CDCl3)δ164.8,151.3,149.1,147.4,140.8,140.7,130.0,129.0,124.5,122.6,121.9,121.9,121.7,121.3,120.6,120.1,117.5,115.0,18.3.
实施例18
干燥的封管中加入金催化剂1a(17.8mg,0.02mmol)，AgOTs(22.3mg,0.08mmol),PhI(OAc)2(129mg,0.4mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(79.1mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应1h。反应液浓缩，干法上样，柱层析得到产物54.1mg(石油醚：乙酸乙酯＝100:1-80:1)，产率65％。1H NMR(500MHz,CDCl3)δ7.71(t,J＝5.0Hz,1H),7.65(d,J＝10.0Hz,2H),7.55-7.50(m,2H),7.49-7.45(m,1H),7.33(d,J＝10.0Hz,2H),5.46(s,1H),3.80(d,J＝10.0Hz,2H),3.69(d,J＝10.0Hz,2H),1.31(s,3H),0.82(s,3H).19F NMR(471MHz,CDCl3)δ-72.76.13C NMR(126MHz,CDCl3)δ149.0,141.6,139.4,139.3,129.0,127.7,126.0,125.1,122.4,121.6,120.1,117.5,115.0,101.4,77.7,30.3,23.1,21.9.HRMS(EI)calcd for C19H19F3O3S(M+):416.0905,found 416.0903.
实施例19
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(46.8mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物34.6mg(石油醚：乙酸乙酯＝3:1)，产率50％。
1H NMR(400MHz,CDCl3)δ8.32(t,J＝4.0Hz,1H),8.15(dt,J＝8.0,4.0Hz,1H),7.82(dt,J＝8.0,4.0Hz,1H),7.70(d,J＝8.0Hz,2H),7.59(t,J＝8.0Hz,1H),7.39(d,J＝8.0Hz,2H).19F NMR(376MHz,CDCl3)δ-72.73.13C NMR(100MHz,CDCl3)δ171.2,149.3,140.4,139.7,132.4,130.1,129.7,129.3,129.0,128.9,123.6,121.9,120.4,117.2,114.0,77.3,77.0,76.7.HRMS m/z(ESI)calcd for C14H10F3NO5S(M+H)+347.0196,found:347.0194.
实施例20
干燥的封管中加入金催化剂1a(8.9mg,0.01mmol)，AgOTs(11.2mg,0.02mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min，随后(59.7mg,0.2mmol)和(73.6mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物56.1mg(石油醚)，产率71％。1H NMR(500MHz,CDCl3)δ7.61(d,J＝8.9Hz,3H),7.41(d,J＝2.3Hz,1H),7.34(d,J＝8.8Hz,2H),7.22(dd,J＝8.2,2.4Hz,1H),2.47(s,3H).19F NMR(471MHz,CDCl3)δ-72.75.13C NMR(125MHz,CDCl3)δ149.0,140.7,138.6,138.5,132.9,129.5,128.7,126.0,125.0,122.6,121.8,120.0,117.5,115.0,23.1,1.0.
实施例21
干燥的封管中加入金催化剂1a(17.8mg,0.02mmol)，AgOTs(22.3mg,0.08mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(59.7mg,0.2mmol)和(77.0mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，干法上样，柱层析得到产物33.5mg(石油醚：乙酸乙酯＝100:1)，产率41％。
1H NMR(400MHz,CDCl3)δ8.30(d,J＝4.0Hz,1H),8.24-8.18(m,1H),7.93(d,J＝8.0Hz,1H),7.91-7.85(m,1H),7.75(d,J＝8.0Hz,2H),7.64(dd,J＝8.0,4.0Hz,1H),7.52-7.47(m,2H),7.40(d,J＝8.0Hz,2H).19F NMR(471MHz,CDCl3)δ-72.71.13C NMR(125MHz,CDCl3)δ148.9,141.7,140.0,139.4,136.2,135.9,135.3,129.1,127.2,125.9,124.6,123.3,123.0,122.6,121.8,121.7,120.1,120.1,117.5,115.0.IR(ATR):ν＝1505.1465,1418,1202,1133,1016,1007,879,844,809,654cm-1.HRMS(EI)calcd for C19H11F3O3S2(M+):408.0102,found 408.0104.
实施例22
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(30.0mg,0.2mmol)和(75.6mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物38.3mg(石油醚：乙酸乙酯＝80:1)，产率74％。1H NMR(400MHz,CDCl3)δ7.90(d,J＝8.0Hz,2H),7.87-7.80(m,2H),7.71(d,J＝8.0Hz,2H),7.68-7.63(m,2H),7.61(t,J＝8.0Hz,1H),7.50(q,J＝8.0Hz,4H),7.41(t,J＝8.0Hz,1H).13C NMR(100MHz,CDCl3)δ196.4,145.2,134.0,137.8,136.2,132.4,130.7,130.0,129.0,128.3,128.2,127.3,127.0.
实施例23
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min.随后(41.7mg,0.2mmol)和(54.0mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物29.5mg(石油醚：乙酸乙酯＝100:1)，产率64％。1H NMR(400MHz,CDCl3)δ8.10(d,J＝8.0Hz,2H),7.65-7.55(m,4H),7.16(t,J＝8.0Hz,2H),3.94(s,3H).19F NMR(376MHz,CDCl3)δ-114.24.13C NMR(100MHz,CDCl3)δ166.9,164.2,161.7,144.6,136.1,136.1,130.2,129.0,128.9,126.9,116.0,115.8,52.2.
实施例24
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(30.0mg,0.2mmol)和(68.0mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物37.1mg(石油醚：乙酸乙酯＝100:1)，产率82％。
1H NMR(500MHz,CDCl3)δ7.61-7.56(m,4H),7.47-7.43(m,2H),7.38-7.34(m,3H),3.73(s,3H),3.69(s,2H).13C NMR(125MHz,CDCl3)δ172.1,140.8,140.1,133.0,129.7,128.8,127.4,127.3,127.1,77.3,77.1,76.8,52.2,40.9.
实施例25
干燥的封管中加入金催化剂1a(12.5mg,0.014mmol)，AgOTs(16.7mg,0.06mmol),PhI(OAc)2(84mg,0.26mmol)和C2H3Cl3(1ml),并在室温条件下剧烈搅拌30min。随后(30.0mg,0.2mmol)和(76.5mg,0.26mmol)的C2H3Cl3(1ml)的混合溶液滴入封管中，在110℃下反应2h。反应液浓缩，通过制备板分离得到产物36.1mg(石油醚：乙酸乙酯＝80:1)，产率70％。
1H NMR(500MHz,CDCl3)δ7.53(d,J＝10.0Hz,2H),7.44(t,J＝10.0Hz,2H),7.41-7.35(m,2H),7.16-7.11(m,2H),3.76(q,J＝5.0Hz,1H),3.71(s,3H),1.54(d,J＝10.0Hz,3H).19F NMR(471MHz,CDCl3)δ-117.62.13C NMR(125MHz,CDCl3)δ174.5,160.7,158.7,141.8,141.8,135.5,130.9,130.8,129.0,128.9,128.5,127.9,127.8,127.7,123.5,123.5,115.3,115.2,52.3,44.9,18.5.

Claims (8)

1.一种卤代联苯类化合物的制备方法，其特征是：它是以FG2和X取代的芳基硼酸酯(2)及FG1和X取代的芳基硅烷试剂(1)为原料，以1,1,2-三氯乙烷作为溶剂，醋酸碘苯((Diacetoxyiodo)benzene)作为氧化剂，对甲苯磺酸银(Silverp-toluenesulfonate)作为银盐，在110℃下，以N-(二苯基磷烷基)-N-异丙基-1,1-二苯基膦胺双核金(Dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine)digold(I))1a作为金催化剂，高效合成保有卤代、FG1基和FG1基的联芳基类化合物。
2.根据权利要求1所述的制备方法，其特征是：所述的FG1基团是氢、烷基、磺酸酯基、炔基、硅醚、醇羟基或甲酸酯基；FG2基团是氢、卤素、醛基、羧酸基、酰胺基或缩醛基；X基团是各种卤素和类卤素。
3.根据权利要求2所述的制备方法，其特征是：所述的类卤素是I、Br、Cl、CN、OTf或OMs基团。
4.根据权利要求1所述的制备方法，其特征是：所述的N-(二苯基磷烷基)-N-异丙基-1,1-二苯基膦胺双核金(1a)有如下结构：
5.根据权利要求1所述的制备方法，其特征是：所述的溶剂1,1,2-三氯乙烷是分子筛预处理过的。
6.根据权利要求1所述的制备方法，其特征是：所述的芳基硅烷试剂和芳基硼酸酯的摩尔比是1:1-1:2。
7.根据权利要求1所述的制备方法，其特征是：所述的金催化剂1a的用量是芳基硅烷试剂1摩尔数的5％-10％；银盐催化剂的用量是芳基硅烷试剂1摩尔数的20％-40％。
8.根据权利要求1所述的制备方法，其特征是：所述的醋酸碘苯是芳基硅烷试剂1摩尔数的1-2倍。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409116A (zh) * 2020-11-27 2021-02-26 温州大学 一种胺基脂肪族硒氰酸酯类化合物的制备方法
CN115504911A (zh) * 2022-09-23 2022-12-23 南京大学 一种对位取代氟苯的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARK D.等: "Gold-Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross-Coupling Reactivity with Gold", 《ANGEW. CHEM. INT. ED.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409116A (zh) * 2020-11-27 2021-02-26 温州大学 一种胺基脂肪族硒氰酸酯类化合物的制备方法
CN112409116B (zh) * 2020-11-27 2023-06-06 温州大学 一种胺基脂肪族硒氰酸酯类化合物的制备方法
CN115504911A (zh) * 2022-09-23 2022-12-23 南京大学 一种对位取代氟苯的制备方法
CN115504911B (zh) * 2022-09-23 2023-10-13 南京大学 一种对位取代氟苯的制备方法

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